1. Field of the Invention
The present invention relates to compounds containing internal unsaturated bonds, more particularly, to polyester ethers.
2. Description of the Prior Art
Hitherto, those compounds containing unsaturated bonds adjacent an aromatic rings, e.g., compounds containing a styryl group or a benzal group, have been widely investigated because of their unique reactivity based on their long conjugated units.
In particular, those compounds containing electron attracting groups at the .beta.-position have been widely studied with respect to polymerizability, photoreactivity, e.g., crosslinking, isomerization, ultraviolet ray filtering functions, etc., chemical reactivity, e.g., amenability to addition reaction, halochromy, etc. Many patents and papers deal with such materials reported, for example, in French Pat. No. 1,482,302, U.S. Pat. No. 2,768,077, Cope, J. Am. Chem. Soc., 63 3452 (1941), Cromwell, J. Org. Chem., 14 411 (1949), Lutz, J. Am. Chem. Soc., 72 4090 (1950), Cohen, J. Chem. Soc., 1964 2,000, Kreisel, J. Poly. Sci., Part A 105 (1964), Schmidt, J. Chem. Soc., 1967 229 to 239, Forward, J. Chem. Soc., Part-C 1969 1868, Hocking, Can. J. Chem., 1969 4567, Marx, T.L., 1971 4957, Whiting, J. Chem. Soc., Part-C 1971 3396, Miller, J. Am. Chem. Soc., 94 3912 (1972), etc.
Furthermore, attempts to produce reactive polymers by providing the characteristics shown by the above low molecular weight compounds to a polymer chain have been made. For example, polymer compounds represented by the formula shown below have been produced from polystyrene, and, in addition, a number of polymer compounds have been synthesized and investigated for photoreactivity, i.e., photocrosslinking capability and photoconductivity. ##STR1## See, for example, U.S. Pat. Nos. 3,257,664, 3,357,831, 3,409,593, 3,418,295, 3,647,447, 3,647,470, 3,737,319, 3,677,754, 3,697,072, 3,748,131, 3,748,144, 3,761,280, 3,767,415, 3,779,989, 2,835,656, British Pat. No. 964,877, J. Kosar, Light Sensitive Systems, John Wiley & Sons, New York (1965), etc.
These investigations have all been directed to introducing internal unsaturated bonds utilizing a polymer reaction.
In this case, however, since the reactions involved are those of polymers, that is, where reactive groups are introduced into polymer compounds, difficulties are encountered in selecting solvents, setting temperatures, and determining the time and amount of the solvent to be applied, etc.
Furthermore, polymer reactions suffer from the defect that the reaction conversion is difficult to increase. In addition, the reaction products isolated are colored, and, thus, operations such as purification, reprecipitation, etc., are required. The reactive polymer compounds obtained also suffer from the defect that it is difficult to modify their reactivity, solubility, film-forming properties, etc., because these properties depend greatly on the characteristics of the polymer compounds initially used (see, for example, E. M. Fettes, Chemical Reactions of Polymers, Interscience Pub., New York (1964), Iwakura et al., Kindai Kogyo Kagaku (Modern Industrial Chemistry), Vol. 16, Part A, on and after page 369, Asakura Shoten, Tokyo (1966), etc.).
Attempts to produce reactive polymers by subjecting addition-polymerizable monomers containing the above internal unsaturated bonds to ionic polymerization or free radical polymerization have been made (see, for example, R. Hart, Markromol, Chem., 37 47 (1960), G. Smetz, Makromol, Chem., 60 89 (1963), Kawai, Kogyo Kagaku Zassi 73 2356 (1970), Kato, J. Poly. Sci., 13 605 (1969), ibid., J. Poly. Sci., A-9 2109 (1971), U.S. Pat. Nos. 3,409,593, 3,453,110, 3,445,545, 3,737,319, 3,770,443, 3,799,915, 3,804,628, British Pat. Nos. 1,231,822, 1,350,516, Japanese Pat. Nos. 48216/1968, 22513/1971, 33074/1972, Japanese Pat. Nos. (OPI) 34794/1972, 55279/1973, 15501/1974, 36794/1974, 38987/1974, etc.).
These methods of producing reactive polymers by utilizing vinyl polymerization reactions have the various problems shown below.
1. The polymerization is liable to be disturbed, and sometimes is substantially inhibited, by moisture (water). PA0 2. If there is present a compound containing an active hydrogen group, e.g., an alcohol, amine, and the like, polymerization is prevented, or a chain transfer reaction takes place with ease, thereby making it difficult to obtain a polymer product. PA0 3. If the polymerization temperature is not maintained at low temperature, e.g., -35 to -78.degree. C., polymerization is sometimes prevented. PA0 4. With an increase in reaction temperature, side reactions take place. PA0 5. Purification of the compounds used is indispensable. PA0 6. Extremely small amounts (on the order of ppm) of impurities. e.g., quinones, sometimes prevent polymerization. PA0 7. In general, polymerization is exothermic, and side reactions are liable to take place due to local heating. PA0 8. Mass production and continuous production are quite difficult. PA0 9. Since the monomer contains two active groups, cross due to side reactions (gellation) takes place. PA0 10. The presence of small amounts of unreacted compounds is inevitable. PA0 11. Reproducibility is poor and molecular weight is liable to change. PA0 1. a carboxy group or functional derivative thereof such as an ester or acid halide and the like PA0 2. hydroxy or functional derivative thereof such as acyloxy and the like. PA0 1. m-.beta.-Hydroxyethoxycinnamic acid PA0 2. m-Methoxy-p-.beta.-hydroxyethoxycinnamic acid PA0 3. p-Methoxy-m-.gamma.-hydroxypropoxycinnamic acid PA0 4. p-Chloro-m-.beta.-hydroxyethoxycinnamic acid PA0 5. o-.beta.-Hydroxyethoxycinnamic acid PA0 6. 1-Hydroxymethyl-3,4-(5 or 6-.beta.-carboxyvinyl)benzodioxane PA0 7. 1-Chloromethyl-3,4-(5 or 6-.beta.-carboxyvinyl) benzodioxane PA0 8. 4-.beta.-Acetoxyethoxycinnamic acid PA0 9. 3-.beta.-Formyloxyethyloxycinnamic acid PA0 10. o-.beta.-Acetoxyethyloxycinnamic acid PA0 11. m-Hydroxyethoxycinnamic acid methyl ester PA0 12. Succinic acid half ester of p-.beta.-hydroxyethoxycinnamic acid PA0 13. p-.delta.-Oxybutoxycinnamic acid PA0 14. 3,5-Dimethoxy-4-(5-oxy-3-oxapentoxy)cinnamic acid PA0 15. o-.omega.-Acetoxybutoxycinnamic acid PA0 16. 2-Methoxy-5-(5-oxy-3-oxapentoxy)cinnamic acid PA0 17. 3-Hydroxypropoxycinnamic acid PA0 18. 2,5-Dimethyl-4-.beta.-hydroxyethoxycinnamic acid PA0 19. o-.beta.-Hydroxypropoxycinnamic acid PA0 20. 2-.beta.-Hydroxyethoxy-5-nitrocinnamic acid PA0 21. 2-.beta.-Hydroxyethoxy-3-chloro-5-nitrocinnamic acid PA0 22. m-.gamma.-Hydroxypropoxycinnamic acid PA0 23. m-Ethoxy-p-.beta.-hydroxyethoxycinnamic acid PA0 24. m-.beta.-Hydroxypropoxycinnamic acid PA0 25. Methyl-m-(9-oxy-1,4,7-trioxa)nonyloxycinnamate PA0 26. 3,5-Dichloro-4-.beta.-hydroxyethoxycinnamic acid PA0 27. m-Chloro-4-.beta.-hydroxyethoxycinnamic acid chloride PA0 28. 4-Hydroxypropoxycinnamic acid chloride PA0 29. Ethyleneglycol-mono(p-.beta.-hydroxyethoxy)cinnamate PA0 30. 2-.beta.-Hydroxyethyl-6-.beta.-methoxycarbonylvinyl naphthalene PA0 31. 4-(p-.beta.-Hydroxyethoxyphenyl)butadiene-1-carboxylic acid PA0 32. 1,2-bis-4-(.beta.-Carboxyvinyl)phenoxyethane PA0 33. 1,2-bis-p-(.beta.-Hydroxyethoxy)cinnamoyloxyethane PA0 34. 1,2-bis-p-Hydroxybutoxycinnamoyloxyethane PA0 35. 1,3-bis-p-Carboxyvinylphenoxypropane PA0 36. 1,4-bis(p-.beta.-Hydroxyethoxycinnamoyloxy)butane
As one method of overcoming these disadvantages inherent to the polymer reaction and the vinyl polymer reaction, a polycondensation reaction can be used.
Most polycondensation reactions utilized in the synthesis of reactive polymers comprise reacting dibasic acids or active derivatives thereof, e.g., esters, acid halides, anhydrides, or the like, with compounds containing two active hydrogens, e.g., diols, alkanolamines, diamines, and the like (see, for example, U.S. Pat. Nos. 3,173,787, 3,453,237, 3,622,320, 3,640,722, 3,647,444, 3,674,745, 3,707,373, 3,726,685, 3,761,250, 3,761,280, 3,775,112, German Pat. Nos. 1,099,732, 1,182,061, 1,229,388, 1,547,794, German Pat. No. (OLS) 2,012,390, British Pat. No. 1,197,182, L. R. Williams, J.A.P.P.S., 15 513, etc.).
These polycondensation reactions, however, suffer from various problems. For example, no high molecular weight polymer is obtained unless dibasic acids and diols are added in equimolar amounts. For this reason, a process is generally used in which diols are used in excess to the acids or esters, and the diols are distilled off from the reaction system as the reaction proceeds so that an equimolar relation is reached, as is well known in processes for obtaining polyethylene terephthalate.
However, even in the case of a diol having the lowest boiling point, i.e., ethylene glycol, its boiling point is about 200.degree. C., and to distil of the ethylene glycol from the system, heating at high temperatures for a long period of time is required. Furthermore, there are the problems that the starting materials, especially the acid component, are of high crystallinity and of a high melting point. For example, a representative unsaturated acid used in U.S. Pat. No. 3,622,320 is paraphenylenediacrylic acid having a melting point of higher than 300.degree. C.
It can be forecast, therefore, that those polyesters produced from dibasic acids having a high melting point are highly crystalline and hard. Such crystallinity, however, is inconvenient in a field where compatibility with tackifiers and additives, solubility, and dyeability are required.
In order to overcome these disadvantages of polyesters produced from dibasic acids of a high melting point, attempts to incorporate dibasic acids of a low melting point as a third component have been made. In U.S. Pat. No. 3,775,112, for example, dibasic acids having a melting point of about 150.degree. C, e.g., azelaic acid, adipic acid, sebacic acid, or the like, are added as third components to decrease the crystallinity of the polyesters obtained, U.S. Pat. No. 3,622,320 also describes adding these low melting point third components in an amount of 12.5 to 42.5 mol% based on the acid component. Even though subjected to such modifications, the polyesters obtained suffer from the defect that they are highly crystalline.
With polymers of such crystallinity, there is a fair possibility of crystallization proceeding due to variations with time during the storage thereof, thereby reducing their compatibility with adhesive additives and their transparency, etc., as a result of which the polymers become brittle. Therefore, in fields in which adherence, compatibility, and affinity are required, e.g, for use as films, adhesives, yarn, filaments, printing plates, compositions, etc., these polymers are used only with difficulty.
In addition, using phenylenediacrylic acid suffers from the disadvantages that phenylenediacrylic acid is not easily available on the market and is high in cost, and that since there is no suitable solvent for recrystallization, purification thereof is difficult.
Furthermore, as is well known in the field of reactive polymers, between the units (C) of reactive units in the polymer compound and the reactivity thereof (S: photocrosslinking capability), there is the relationship that S is almost proportional to the square of C (see, for example, C. C. Unruh, J. Appl. Poly. Sci., 2 358 (1959), M. Thuda, J. Poly. Sci., A-2 2911 (1964), etc.).
From this relationship, it can be forecast that a decrease in the phenylenediacrylic acid present (corresponding to (C)) will cause a sudden reduction in the reactivity of the polyester, and thus suitability thereof as a material for a printing plate, relief image, and the like is lost.
Therefore, a reduction in crystallinity by the addition of third components as described in the above patents is attended by a decrease in the most important feature of reactivity, which is quite disadvantageous.
As a result of the inventor's research on the above points, the use of compounds containing two kinds of reactive groups, one being a cinnamic acid skelton of high reactivity and the other being a skelton capable of forming a polyester ether on application of one stage processing, e.g., heating, an ester exchange reaction, treatment with a base, etc., has been discovered. That is, the use of compounds containing two kinds of reactive groups enables the above problems encountered in producing polyesters from dibasic acids to be overcome. Furthermore, it has been found that the use of such compounds provides polymers of any desired degree of crystallinity as necessary. In addition, the production of polyester ethers comprising only the above component (C) becomes possible, and a considerable improvement in the reactivity of the polyester ethers obtained is achieved.